A method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction

Abstract

The present invention relates to a method for preparing a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction, comprising: based on a solid phase method, using barium carbonate and tungsten trioxide to prepare a pure phase of barium tungstate; granulating and tableting the pure phase of barium tungstate in sequence to obtain a barium tungstate sample sheet; calcining the barium tungstate sample sheet at different temperatures to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction. The barium tungstate ceramic self-catalytic electrode obtained by this preparation method is not only low in cost and convenient to prepare, but also has large pores between the formed grains, exposing more active sites, which is conducive to the transmission of ions; and the ceramic itself has strong stability and corrosion resistance, overcomes the problem of poor stability of traditional electrodes, and improves long-cycle stability.

Description

Technical Field

[0001] The invention relates to the field of materials and energy technology, and in particular to a method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction. Background Art

[0002] Developing clean energy to replace traditional energy has become a trend in global energy development. Hydrogen energy is regarded as an ideal candidate for new energy due to its carbon-free emissions, high energy density and renewability, and is hailed as the "ultimate energy of the 21st century". Among various hydrogen production methods, water electrolysis is an effective solution to obtain clean, high-energy-density hydrogen energy. The water electrolysis reaction can use intermittent solar energy and wind energy as energy to start the reaction, and obtain high-purity hydrogen for use in industrial fields such as fuel cells. However, the electrochemical kinetics of the hydrogen evolution reaction (HER), a half-reaction of water electrolysis, is slow, resulting in high energy consumption during actual work of water electrolysis. Therefore, in order to reduce the catalytic reaction energy barrier and increase the reaction rate, it is necessary to explore an efficient water electrolysis catalyst.

[0003] So far, precious metal materials, mainly represented by platinum group metals, are considered to be the most advanced electrocatalysts for HER due to their high intrinsic catalytic activity, but their large-scale industrial use is seriously hindered by their high price, scarcity and poor durability. Therefore, there is an urgent need to develop low-cost, highly stable and catalytically active water electrolysis catalysts. At present, the selection and design of catalyst materials are difficult problems faced by the field of electrocatalysis. It is challenging to rationally design and prepare low-cost and high-efficiency catalyst materials for water electrolysis.

[0004] Therefore, designing and preparing an electrocatalyst material with high activity, high stability, corrosion resistance, and low cost and availability has become an effective method to deal with industrial water electrolysis. Summary of the invention

[0005] In order to solve the above problems existing in the prior art, the present invention provides a method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction. The technical problem to be solved by the present invention is achieved by the following technical solution:

[0006] The present invention provides a method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction, the preparation method comprising:

[0007] Based on the solid phase method, pure phase barium tungstate is prepared using barium carbonate and tungsten trioxide chemicals;

[0008] The pure phase of barium tungstate is granulated and tabletted in sequence to obtain a barium tungstate sample tablet;

[0009] The barium tungstate sample sheet is calcined at different temperatures to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0010] In one embodiment of the present invention, based on the solid phase method, a pure phase of barium tungstate is prepared using a barium carbonate chemical and a tungsten trioxide chemical, including:

[0011] Mixing the barium carbonate drug and the tungsten trioxide drug according to a preset molar ratio to obtain a first mixed drug;

[0012] Adding deionized water and zirconium balls to the mixed medicine according to a preset ratio to obtain a second mixed medicine;

[0013] ball milling the second mixed medicine to obtain a mixed solution;

[0014] Drying the mixed solution to obtain a dried sample;

[0015] The dried sample is sieved to remove zirconium balls in the sample to obtain sample powder;

[0016] The sample powder is calcined to obtain the pure phase of barium tungstate.

[0017] In one embodiment of the present invention, the preset molar ratio is 1:0.8-1.2 of the barium carbonate chemical to the tungsten trioxide chemical.

[0018] In one embodiment of the present invention, the preset ratio is that the mass ratio of deionized water, the first mixed medicine and the zirconium balls is 4:1:1.

[0019] In one embodiment of the present invention, the sample powder is calcined to obtain the pure phase of barium tungstate, including:

[0020] The sample powder is placed in a crucible, and the temperature is raised to 850-900° C. at a rate of 2-5° C. / min in a muffle furnace. The sample powder is kept at 850-900° C. for 6-10 hours to obtain the pure phase of barium tungstate.

[0021] In one embodiment of the present invention, the pure phase of barium tungstate is granulated and tabletted in sequence to obtain a barium tungstate sample tablet, comprising:

[0022] Grinding the pure phase of barium tungstate to obtain first particles;

[0023] During the grinding process, a PVA binder is added dropwise to the first particles for multiple times to obtain second particles;

[0024] The second particles are sieved to obtain third particles with a mesh size of 80 to 120;

[0025] Weigh 0.6-0.8 g of the third particle;

[0026] Under a pressure of 6 to 15 MPa, the weighed third particles are pressed for 1 to 3 minutes to obtain the barium tungstate sample sheet.

[0027] In one embodiment of the present invention, during the grinding process, a PVA binder is added to the first particles multiple times to obtain second particles, comprising:

[0028] During the grinding process, one drop of the PVA binder is dripped onto the first particles every 2 to 5 minutes to obtain the second particles, wherein the total dripping amount of the PVA binder is 3 to 8 ml, and the total dripping time is 1 to 2 hours.

[0029] In one embodiment of the present invention, the barium tungstate sample sheet is calcined at different temperatures to obtain a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction, comprising:

[0030] calcining the barium tungstate sample sheet at a first temperature to obtain a calcined barium tungstate sample sheet;

[0031] The calcined barium tungstate sample sheet is calcined at a second temperature to obtain the barium tungstate ceramic self-catalytic electrode, wherein the second temperature is greater than the first temperature.

[0032] In one embodiment of the present invention, the barium tungstate sample sheet is calcined at a first temperature to obtain a calcined barium tungstate sample sheet, comprising:

[0033] The barium tungstate sample piece is placed in a crucible, and the temperature is raised to 600-800° C. at a rate of 2-5° C. / min in a muffle furnace. The barium tungstate sample piece is kept at 600-800° C. for 2-5 hours to obtain the calcined barium tungstate sample piece.

[0034] In one embodiment of the present invention, the calcined barium tungstate sample sheet is calcined at a second temperature to obtain the barium tungstate ceramic autocatalytic electrode, comprising:

[0035] The calcined barium tungstate sample piece is placed in a crucible, and the temperature is raised to 1075° C. at a rate of 2-5° C. / min in a muffle furnace. The calcined barium tungstate sample piece is kept at 1075° C. for 2-5 hours to obtain the barium tungstate ceramic self-catalytic electrode.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] The present invention first prepares pure barium tungstate phase using barium carbonate and tungsten trioxide based on the solid phase method, then sequentially granulates and tablets the pure barium tungstate phase to obtain barium tungstate sample sheets, and finally calcines the barium tungstate sample sheets at different temperatures to obtain barium tungstate ceramic self-catalytic electrodes for efficient hydrogen evolution reaction. The barium tungstate ceramic self-catalytic electrode obtained by this preparation method is not only low-cost and easy to prepare, but also has large pores between the formed grains, exposing more active sites, which is conducive to the transmission of ions; and the ceramic itself has strong stability and corrosion resistance, overcomes the problem of poor stability of traditional electrodes, and improves long-cycle stability.

[0038] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 A schematic flow chart of a method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction provided by an embodiment of the present invention;

[0040] Figure 2 The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared in Example 2 of the present invention is a HER linear sweep voltammogram of the barium tungstate ceramic material at 1050° C. in a 1.0 mol / L potassium hydroxide electrolyte at a scan rate of 5 mV per second;

[0041] Figure 3 The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared in Example 3 of the present invention is a HER linear scanning voltammogram of the barium tungstate ceramic material at 1075° C. in a 1.0 mol / L potassium hydroxide electrolyte at a scanning rate of 5 mV per second;

[0042] Figure 4 This is a scanning electron microscope image of the barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared in Example 3 of the present invention;

[0043] Figure 5 This is a scanning electron microscope image of the barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared in Example 3 of the present invention;

[0044] Figure 6 This is a transmission electron microscope image of the barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared in Example 3 of the present invention;

[0045] Figure 7 This is an X-ray diffraction spectrum analysis diagram of the barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared in Example 3 of the present invention;

[0046] Figure 8The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared in Example 4 of the present invention is a HER linear sweep voltammogram of the barium tungstate ceramic material at 1100° C. in a 1.0 mol / L potassium hydroxide electrolyte at a scan rate of 5 mV per second;

[0047] Fig. 9 The actual pictures are of the barium tungstate ceramic self-catalytic electrode obtained by calcining at 1050° C., 1075° C. and 1100° C. respectively using the preparation method of an embodiment of the present invention. DETAILED DESCRIPTION

[0048] The present invention is further described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.

[0049] Embodiment 1

[0050] Ceramic materials have the characteristics of high temperature stability, corrosion resistance, and high mechanical strength. These characteristics make ceramic materials promising to become a highly stable and active electrocatalytic material. The basic principle of ceramic electrocatalytic technology is to use electrochemical reactions to achieve catalysis. In electrochemical reactions, electrons and ions undergo redox reactions on the electrode surface, thereby generating current and chemical reaction products. Ceramic electrocatalytic technology uses catalysts on the electrode surface to promote electrochemical reactions, thereby increasing reaction rates and efficiency.

[0051] See also Figure 1 , Figure 1 The present invention provides a method for preparing a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction, and the method comprises:

[0052] Step 1: Based on the solid phase method, pure phase of barium tungstate (BaWO4) is prepared using barium carbonate and tungsten trioxide.

[0053] Step 1.1, mixing the barium carbonate drug and the tungsten trioxide drug according to a preset molar ratio to obtain a first mixed drug.

[0054] Optionally, the preset molar ratio of the barium carbonate chemical to the tungsten trioxide chemical is 1:0.8-1.2.

[0055] Preferably, the molar ratio of the barium carbonate chemical to the tungsten trioxide chemical is 1:1.

[0056] For example, 0.025 mol of a barium carbonate chemical and 0.025 mol of a tungsten trioxide chemical are mixed in equal molar amounts to obtain a first mixed chemical.

[0057] Step 1.2, adding deionized water and zirconium balls to the mixed medicine according to a preset ratio to obtain a second mixed medicine.

[0058] Preferably, the preset ratio is that the mass ratio of deionized water, the first mixed medicine and the zirconium balls is 4:1:1.

[0059] That is to say, deionized water and zirconium balls are added to the second mixed medicine in a certain mass ratio, zirconium balls: second mixed medicine: deionized water = 4:1:1.

[0060] For example, the zirconium ball is 40 to 50 g, and the deionized water is 10 to 15 mL.

[0061] Step 1.3: ball milling the second mixed medicine to obtain a mixed solution.

[0062] Specifically, the second mixed medicine is put into a ball mill for ball milling. The ball milling time is 4 to 10 hours, and the rotation speed is, for example, 300 to 600 revolutions / min. After the ball milling is completed, a mixed solution is obtained.

[0063] Step 1.4, drying the mixed solution to obtain a dried sample.

[0064] Specifically, the mixed solution obtained after ball milling is poured into a glass dish, and dried in an oven at a temperature of 60 to 90° C. for 3 to 6 hours to obtain a dried sample.

[0065] Step 1.5: Sieve the dried sample to remove the zirconium balls in the sample to obtain sample powder.

[0066] Step 1.6: calcine the sample powder to obtain a pure phase of barium tungstate.

[0067] Specifically, the sample powder is put into a crucible, and the temperature is raised to 850-900° C. at a rate of 2-5° C. / min in a muffle furnace, and the sample powder is kept at 850-900° C. for 6-10 hours to obtain a pure phase of barium tungstate.

[0068] The purpose of calcining the sample powder is to produce a chemical reaction so that barium carbonate and tungsten trioxide react to obtain a pure phase of barium tungstate. Under the temperature condition of 850-900°C, barium carbonate and tungsten trioxide can fully react without producing other impurities.

[0069] Step 2: The pure phase of barium tungstate is granulated and tabletted in sequence to obtain a barium tungstate sample tablet.

[0070] Step 2.1: Grind the pure phase of barium tungstate to obtain first particles.

[0071] Specifically, the pure phase of barium tungstate obtained by calcination is put into a mortar and ground for 2 to 5 minutes to obtain fine particles, namely, the first particles.

[0072] Step 2.2: During the grinding process, PVA (polyvinyl alcohol) binder is added dropwise to the first particles for multiple times to obtain second particles.

[0073] Specifically, during the grinding process, a drop of PVA binder is added to the first particles every 2 to 5 minutes to obtain second particles, wherein the total amount of the PVA binder added is 3 to 8 ml, and the total adding time is 1 to 2 hours.

[0074] Step 2.3, sieving the second particles to obtain third particles of 80-120 mesh.

[0075] Specifically, the second granules obtained after granulation are sieved with 80 mesh and 120 mesh to obtain third granules with 80-120 mesh.

[0076] Step 2.4, weigh 0.6-0.8 g of the third granule.

[0077] Specifically, the third particles obtained in step 2.3 are weighed using a balance, and the weighed mass is 0.6 to 0.8 g.

[0078] Step 2.5: Press the weighed third particles for 1 to 3 minutes under a pressure of 6 to 15 MPa to obtain a barium tungstate sample sheet.

[0079] Specifically, the third particles weighed in step 2.4 are placed in a tablet press, the pressure is 6 to 15 MPa, the time is 1 to 3 min, and the weighed third particles are pressed to obtain barium tungstate sample tablets.

[0080] Step 3: calcining the barium tungstate sample sheets at different temperatures to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0081] Step 3.1: calcining the barium tungstate sample sheet at a first temperature to obtain a calcined barium tungstate sample sheet.

[0082] Step 3.2: calcining the calcined barium tungstate sample sheet at a second temperature to obtain a barium tungstate ceramic self-catalytic electrode, wherein the second temperature is greater than the first temperature.

[0083] The purpose of calcining the barium tungstate sample sheet at a first lower temperature is to remove adhesives (ie, to remove PVA), and the purpose of calcining the barium tungstate sample sheet at a second higher temperature is to convert it into a ceramic phase.

[0084] In a specific embodiment, step 3.1 may specifically include:

[0085] The barium tungstate sample piece is placed in a crucible, and the temperature is raised to 600-800°C at a rate of 2-5°C / min in a muffle furnace. The barium tungstate sample piece is kept at 600-800°C for 2-5 hours to obtain a calcined barium tungstate sample piece.

[0086] By keeping the barium tungstate sample sheet at 600-800℃ for 2-5h, PVA can be completely discharged.

[0087] In a specific embodiment, step 3.2 may specifically include:

[0088] The calcined barium tungstate sample piece is placed in a crucible, and the temperature is raised to 1075°C at a rate of 2-5°C / min in a muffle furnace. The calcined barium tungstate sample piece is kept at 1075°C for 2-5h to obtain a barium tungstate ceramic self-catalytic electrode.

[0089] Keeping the calcined barium tungstate sample at 1075°C for 2 to 5 hours can make the calcined barium tungstate sample form a ceramic phase. A large number of experiments have shown that the performance of the calcined barium tungstate sample is best when it is calcined again at 1075°C.

[0090] The preparation method adopted by the present invention is simple and easy to operate, and a water electrolysis catalyst with high efficiency, low cost and good stability can be prepared by a solid phase method.

[0091] The barium tungstate ceramic self-catalytic electrode obtained by the present invention is not only low in cost and easy to prepare, but also generates gas and defects inside the ceramic due to the influence of the heating rate during sintering; at the same time, in the process of grain growth, since each grain is heated differently, the grain growth is also not the same, so large pores are generated, exposing more active sites, and the pores provide channels for the transmission of ions, which is beneficial to the transmission of ions and improves the electrochemical performance; and the ceramic itself has strong stability and corrosion resistance, overcomes the problem of poor stability of traditional electrodes, and improves long-cycle stability.

[0092] Therefore, the preparation method of the barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction provided by the present invention overcomes the problems of low efficiency, high cost, low catalytic activity, poor stability and difficulty in industrial production of electrocatalytic materials. The barium tungstate electrocatalytic functional ceramic material prepared by the present invention not only has many active sites and good electrocatalytic performance, but also has a simple preparation process, is corrosion-resistant, has good stability, is low in cost, and can be prepared on a large scale. It is a new low-cost and high-efficiency preparation method.

[0093] Embodiment 2

[0094] The embodiment of the present invention provides a specific method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction on the basis of the first embodiment. The preparation method comprises:

[0095] S2.1. Prepare pure phase of barium tungstate by solid phase method.

[0096] Specifically, first, 0.025 mol of barium carbonate and 0.025 mol of tungsten trioxide are mixed in equal molar amounts to obtain a first mixed drug; deionized water and zirconium balls are added to the first mixed drug according to a certain mass ratio to obtain a second mixed drug, zirconium balls: first mixed drug: deionized water = 4:1:1, zirconium balls are 40-50 g, deionized water is 10-15 mL; then the second mixed drug is put into a ball mill for ball milling, the ball milling time is 4-10 hours, the speed is 300 rpm, and a mixed solution is obtained. The mixed solution obtained after ball milling is poured into a glass dish and dried in an oven at a temperature of 80°C for 3-6 hours; the dried sample is sieved to remove the zirconium balls in the sample to obtain a sample powder; then the sample powder is put into a crucible, and the temperature is raised to 860°C at a rate of 2°C / min in a muffle furnace, and the temperature is kept for 6 hours to obtain a pure phase of barium tungstate.

[0097] S2.2, granulate and tablet the pure phase of barium tungstate.

[0098] Specifically, the pure phase of barium tungstate obtained in S2.1 is put into a mortar for grinding to obtain fine first particles; then granulation is performed, which is also performed in the mortar, that is, 6% PVA binder is added in small amounts several times during the grinding process to obtain second particles; after granulation, the obtained second particles are sieved with 80 mesh and 120 mesh to obtain third particles of 80-120 mesh; the third particles are weighed with a balance, and the mass is 0.6-0.8g; then the weighed third particles are put into a tablet press, the pressure is 6-15MPa, and the time is 1-3min to obtain barium tungstate sample tablets.

[0099] S2.3. Preparation of barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction at different temperature gradients.

[0100] Specifically, the barium tungstate sample sheet was placed in a crucible and calcined at different temperatures in a muffle furnace. First, the temperature was increased to 600°C at a heating rate of 5°C / min and kept at this temperature for 2 hours. Then, the temperature was increased to 1050°C at the same heating rate and kept at this temperature for 2 hours to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0101] The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention is used as a catalyst in the following specific steps: the prepared barium tungstate ceramic self-catalytic electrode material is clamped on a platinum electrode clamp directly as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The electrochemical performance of HER is tested in a 1.0M KOH solution at room temperature and pressure. The test results are as follows: Figure 2 As shown, in a 1.0M KOH alkaline solution, the material in this embodiment has a -2 At a current density of , the overpotential of HER on the barium tungstate ceramic self-catalytic electrode is 350 mV at 1050°C.

[0102] The preparation method of the barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction provided by the present invention overcomes the problems of low efficiency, high cost, low catalytic activity, poor stability and difficulty in industrial production of electrocatalytic materials. The barium tungstate electrocatalytic functional ceramic material prepared by the present invention not only has many active sites and good electrocatalytic performance, but also has a simple preparation process, is corrosion-resistant, low cost, and can be prepared on a large scale. It is a new low-cost and high-efficiency preparation method.

[0103] Embodiment 3

[0104] The embodiment of the present invention provides another specific method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction based on the first embodiment. The preparation method comprises:

[0105] S3.1. Prepare pure phase of barium tungstate by solid phase method.

[0106] Specifically, first, 0.025 mol of barium carbonate and 0.025 mol of tungsten trioxide are mixed in equal molar amounts to obtain a first mixed drug; deionized water and zirconium balls are added to the first mixed drug according to a certain mass ratio to obtain a second mixed drug, zirconium balls: second mixed drug: deionized water = 4:1:1, zirconium balls are 40-50g, deionized water is 10-15mL; then the second mixed drug is put into a ball mill for ball milling, the ball milling time is 4-10h, the speed is 300 rpm, and a mixed solution is obtained. The mixed solution obtained after ball milling is poured into a glass dish and dried in an oven at a temperature of 80°C for 3-6h; the dried sample is sieved to remove the zirconium balls in the sample to obtain a sample powder; then it is placed in a crucible, heated to 860°C at a rate of 2°C / min in a muffle furnace, and kept warm for 6h to obtain a pure phase of barium tungstate.

[0107] S3.2, granulate and tablet the pure phase of barium tungstate.

[0108] Specifically, the pure phase of barium tungstate obtained in S3.1 is put into a mortar for grinding to obtain fine first particles; then granulation is performed, which is also performed in the mortar, that is, 6% PVA binder is added in small amounts several times during the grinding process to obtain second particles; after granulation, the obtained second particles are sieved with 80 mesh and 120 mesh to obtain third particles of 80-120 mesh; the third particles are weighed with a balance, and the mass is 0.6-0.8g; then the weighed third particles are put into a tablet press, the pressure is 6-15MPa, and the time is 1-3min to obtain barium tungstate sample tablets.

[0109] S3.3. Preparation of barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction at different temperature gradients.

[0110] Specifically, the barium tungstate sample sheet was placed in a crucible and calcined at different temperatures in a muffle furnace. First, the temperature was increased to 600°C at a heating rate of 5°C / min and kept at this temperature for 2 hours. Then, the temperature was increased to 1075°C at the same heating rate and kept at this temperature for 2 hours to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0111] The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention is used as a catalyst in the following specific steps: the prepared barium tungstate ceramic self-catalytic electrode material is clamped on a platinum electrode clamp directly as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The electrochemical performance of the HER is tested in a 1.0M KOH solution at room temperature and pressure. In a 1.0M KOH alkaline solution, the material in this embodiment has a HER of 10 mA cm -2 At a current density of 1000 ℃, the overpotential of the HER of the barium tungstate ceramic self-catalytic electrode is 272 mV at 1075 ℃. Figure 3 As shown, in a 1.0 M KOH alkaline solution, the material in this embodiment has a -2 At a current density of 1000 ℃, the overpotential of the HER of the barium tungstate ceramic self-catalytic electrode at 1075 ℃ is 272 mV. Therefore, good performance is shown at 1075 ℃, which reveals that the barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention can maintain a high electrolysis efficiency of water without using precious metals. The material in this embodiment was subjected to 10 cycles of LSV and characterized by scanning electron microscopy. Figure 4 As shown, the barium tungstate ceramic self-catalytic electrode in this embodiment still maintains a stable structure without any obvious changes, which indicates that the material has extremely strong stability.

[0112] The scanning electron microscope (SEM) image of the composite material prepared in this example is as follows: Figure 5As shown, it can be observed that the surface of the barium tungstate ceramic has obvious pores, which is conducive to the transmission of ions. At the same time, it provides a larger specific surface area, exposes more active sites, and has better catalytic performance. In order to further observe the existence form of BaWO4, the material of this example can be observed under a transmission electron microscope (TEM), as shown in FIG. Figure 6 As shown in the figure, the lattice fringes of BaWO4 ceramics are 0.33nm. In addition, XRD phase characterization of the material obtained in Example 3 is also carried out, and the results are as follows: Figure 7 As shown, there is a strong characteristic peak of barium tungstate on the substrate, and the peak belonging to BaWO4 at about 26° can be identified. According to the characterization diagram, it can be seen that the prepared sample has no other impurity phases.

[0113] Embodiment 4

[0114] The embodiment of the present invention provides another specific method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction based on the first embodiment. The preparation method comprises:

[0115] S4.1. Prepare pure phase of barium tungstate by solid phase method.

[0116] Specifically, first, 0.025 mol of barium carbonate and 0.025 mol of tungsten trioxide are mixed in equal molar amounts to obtain a first mixed drug; deionized water and zirconium balls are added to the first mixed drug according to a certain mass ratio to obtain a second mixed drug, zirconium balls: first mixed drug: deionized water = 4:1:1, zirconium balls are 40-50 g, deionized water is 10-15 mL; then the second mixed drug is put into a ball mill for ball milling, the ball milling time is 4-10 hours, the speed is 300 rpm, and a mixed solution is obtained. The mixed solution after ball milling is poured into a glass dish and dried in an oven at a temperature of 80°C for 3-6 hours; the dried sample is sieved to remove the zirconium balls in the sample to obtain a sample powder; then the sample powder is put into a crucible, heated to 860°C at a rate of 2°C / min in a muffle furnace, and kept warm for 6 hours to obtain a pure phase of barium tungstate.

[0117] S4.2. Granulate and tablet the pure phase of barium tungstate.

[0118] Specifically, the pure phase of barium tungstate obtained in S4.1 is put into a mortar for grinding to obtain fine first particles; then granulation is performed, which is also performed in the mortar, that is, 6% PVA binder is added in small amounts several times during the grinding process to obtain second particles; after granulation, the obtained second particles are sieved with 80 mesh and 120 mesh to obtain third particles of 80-120 mesh; the third particles are weighed with a balance, and the mass is 0.6-0.8g; then the weighed third particles are put into a tablet press, the pressure is 6-15MPa, and the time is 1-3min to obtain barium tungstate sample tablets.

[0119] S4.3. Preparation of barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction at different temperature gradients.

[0120] Specifically, a barium tungstate sample sheet was placed in a crucible and calcined at different temperatures in a muffle furnace. First, the temperature was increased to 600°C at a heating rate of 5°C / min and kept at this temperature for 2 hours. Then, the temperature was increased to 1100°C at the same heating rate and kept at this temperature for 2 hours to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0121] The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention is used as a catalyst in the following specific steps: the prepared barium tungstate ceramic self-catalytic electrode material is clamped on a platinum electrode clamp directly as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The electrochemical performance of HER is tested in a 1.0M KOH solution at room temperature and pressure. The test results are as follows: Figure 8 As shown, in a 1.0M KOH alkaline solution, the material in this embodiment has a -2 At a current density of , the overpotential of HER of the barium tungstate ceramic self-catalytic electrode at 1100°C is 347mV.

[0122] The advantages of the present invention are: (1) the barium tungstate ceramic self-catalytic electrode material has a relatively stable structure and a large specific surface area, so that it can maintain a high catalytic activity, excellent stability and excellent compressive resistance in electrocatalytic applications; (2) the barium tungstate ceramic self-catalytic electrode material in the present invention, when used as an electrocatalyst for hydrogen evolution reaction, shows excellent electrocatalytic properties (HER overpotential at 1100°C in 1.0M KOH solution: η10mA cm -2 =347mV).

[0123] Embodiment 5

[0124] The embodiment of the present invention provides another specific method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction based on the first embodiment. The preparation method comprises:

[0125] S5.1. Prepare pure phase of barium tungstate by solid phase method.

[0126] Specifically, first, 0.025 mol of barium carbonate and 0.025 mol of tungsten trioxide are mixed in equal molar amounts to obtain a first mixed drug; deionized water and zirconium balls are added to the first mixed drug according to a certain mass ratio to obtain a second mixed drug, zirconium balls: first mixed drug: deionized water = 4:1:1, zirconium balls are 40-50 g, deionized water is 10-15 mL; then the second mixed drug is put into a ball mill for ball milling, the ball milling time is 4-10 hours, the speed is 300 rpm, and a mixed solution is obtained. The mixed solution obtained after ball milling is poured into a glass dish and dried in an oven at a temperature of 80°C for 3-6 hours; the dried sample is sieved to remove the zirconium balls in the sample to obtain a sample powder; then the sample powder is put into a crucible, and the temperature is raised to 860°C at a rate of 2°C / min in a muffle furnace, and the temperature is kept for 6 hours to obtain a pure phase of barium tungstate.

[0127] S5.2. Granulate and tablet the pure phase of barium tungstate.

[0128] Specifically, the pure phase of barium tungstate obtained in S5.2 is put into a mortar for grinding to obtain fine first particles; then granulation is performed, which is also performed in the mortar, that is, 10% of the PVA binder is added in small amounts several times during the grinding process to obtain second particles; after granulation, the obtained second particles are sieved with a sieve of 80 mesh and 120 mesh to obtain third particles of 80-120 mesh; the third particles are weighed with a balance, and the mass is 0.6-0.8g; then the weighed third particles are put into a tablet press, the pressure is 6-15MPa, and the time is 1-3min to obtain barium tungstate sample tablets.

[0129] S5.3. Preparation of barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction at different temperature gradients.

[0130] Specifically, the barium tungstate sample sheet was placed in a crucible and calcined at different temperatures in a muffle furnace. First, the temperature was increased to 600°C at a heating rate of 5°C / min and kept at this temperature for 2 hours. Then, the temperature was increased to 1050°C at the same heating rate and kept at this temperature for 2 hours to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0131] The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention is used as a catalyst, and the specific steps are: the prepared barium tungstate ceramic self-catalytic electrode material is clamped on a platinum electrode clamp directly as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The electrochemical performance of HER is tested in a 1.0M KOH solution at room temperature and pressure.

[0132] The barium tungstate ceramic self-catalytic electrode material in this embodiment changes the content and temperature of PVA, and the target product obtained still has a stable and uniform structure, which further illustrates that the process used in the present invention is simple and stable, and the process can be adjusted according to different requirements.

[0133] Embodiment 6

[0134] The embodiment of the present invention provides another specific method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction based on the first embodiment. The preparation method comprises:

[0135] S6.1. Prepare pure phase of barium tungstate by solid phase method.

[0136] Specifically, first, 0.025 mol of barium carbonate and 0.025 mol of tungsten trioxide are mixed in equal molar amounts to obtain a first mixed drug; deionized water and zirconium balls are added to the first mixed drug according to a certain mass ratio, zirconium balls: first mixed drug: deionized water = 4:1:1, zirconium balls are 40-50 g, deionized water is 10-15 mL; then put into a ball mill for ball milling, the ball milling time is 4-10 hours, the speed is 300 rpm, and a mixed solution is obtained. The mixed solution obtained after ball milling is poured into a glass dish and dried in an oven at a temperature of 80°C for 3-6 hours; the dried sample is sieved to remove the zirconium balls in the sample to obtain a sample powder; then the sample powder is placed in a crucible and heated to 860°C at a rate of 2°C / min in a muffle furnace, and kept warm for 6 hours to obtain a pure phase of barium tungstate.

[0137] S6.2. The pure BaWO4 phase is granulated and tableted.

[0138] Specifically, the pure phase of barium tungstate obtained in S6.1 is put into a mortar for grinding to obtain fine first particles; then granulation is performed, which is also performed in the mortar, that is, 10% PVA binder is added in small amounts several times during the grinding process to obtain second particles; after granulation, the obtained second particles are sieved with 80 mesh and 120 mesh to obtain third particles of 80-120 mesh; the third particles are weighed with a balance, and the mass is 0.6-0.8g; then the weighed third particles are put into a tablet press, the pressure is 6-15MPa, and the time is 1-3min to obtain barium tungstate sample tablets.

[0139] S6.3. Preparation of barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction at different temperature gradients.

[0140] Specifically, the barium tungstate sample sheet was placed in a crucible and calcined at different temperatures in a muffle furnace. First, the temperature was increased to 600°C at a heating rate of 5°C / min and kept at this temperature for 2 hours. Then, the temperature was increased to 1075°C at the same heating rate and kept at this temperature for 2 hours to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0141] The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention is used as a catalyst, and the specific steps are: the prepared barium tungstate ceramic self-catalytic electrode material is clamped on a platinum electrode clamp directly as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The electrochemical performance of HER is tested in a 1.0M KOH solution at room temperature and pressure.

[0142] Embodiment 7

[0143] The embodiment of the present invention provides another specific method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction based on the first embodiment. The preparation method comprises:

[0144] S7.1. Prepare pure phase of barium tungstate by solid phase method.

[0145] Specifically, first, 0.025 mol of barium carbonate and 0.025 mol of tungsten trioxide are mixed in equal molar amounts to obtain a first mixed drug; deionized water and zirconium balls are added to the first mixed drug according to a certain mass ratio to obtain a second mixed drug, zirconium balls: first mixed drug: deionized water = 4:1:1, zirconium balls are 40-50g, deionized water is 10-15mL; then put it into a ball mill for ball milling, the ball milling time is 4-10h, the speed is 300 rpm, and a mixed solution is obtained. The ball-milled mixture is poured into a glass dish and dried in an oven at a temperature of 80°C for 3-6h; the dried sample is sieved to remove the zirconium balls in the sample to obtain a sample powder; then it is placed in a crucible and heated to 860°C at a rate of 2°C / min in a muffle furnace, and kept warm for 6h to obtain a pure phase of barium tungstate.

[0146] S7.2. Granulate and tablet the pure phase of barium tungstate.

[0147] Specifically, the pure phase of barium tungstate obtained in S7.1 is put into a mortar for grinding to obtain fine first particles; then granulation is performed, which is also performed in the mortar, that is, 10% PVA binder is added in small amounts several times during the grinding process to obtain second particles; after granulation, the obtained second particles are sieved with 80 mesh and 120 mesh to obtain third particles of 80-120 mesh; the third particles are weighed with a balance, and the mass is 0.6-0.8g; then the weighed third particles are put into a tablet press, the pressure is 6-15MPa, and the time is 1-3min to obtain barium tungstate sample tablets.

[0148] S7.3. Preparation of barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction at different temperature gradients.

[0149] Specifically, a barium tungstate sample sheet was placed in a crucible and calcined at different temperatures in a muffle furnace. First, the temperature was increased to 600°C at a heating rate of 5°C / min and kept at this temperature for 2 hours. Then, the temperature was increased to 1100°C at the same heating rate and kept at this temperature for 2 hours to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0150] The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention is used as a catalyst, and the specific steps are: the prepared barium tungstate ceramic self-catalytic electrode material is clamped on a platinum electrode clamp directly as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The electrochemical performance of HER is tested in a 1.0M KOH solution at room temperature and pressure.

[0151] Embodiment 8

[0152] The embodiment of the present invention provides another specific method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction based on the first embodiment. The preparation method comprises:

[0153] S8.1. Prepare pure phase of barium tungstate by solid phase method.

[0154] Specifically, first, 0.025 mol of barium carbonate and 0.020 mol of tungsten trioxide are mixed in equal molar amounts to obtain a first mixed drug; deionized water and zirconium balls are added to the first mixed drug according to a certain mass ratio to obtain a second mixed drug, zirconium balls: first mixed drug: deionized water = 4:1:1, zirconium balls are 40-50g, deionized water is 10-15mL; then the second mixed drug is put into a ball mill for ball milling, the ball milling time is 4-10h, the speed is 300 rpm, and a mixed solution is obtained. The mixed solution obtained after ball milling is poured into a glass dish and dried in an oven at a temperature of 80°C for 3-6h; the dried sample is sieved to remove the zirconium balls in the sample to obtain a sample powder; then the sample powder is put into a crucible, and the temperature is raised to 860°C at a rate of 2°C / min in a muffle furnace, and kept warm for 6h to obtain a pure phase of barium tungstate.

[0155] S8.2. Granulate and tablet the pure phase of barium tungstate.

[0156] Specifically, the pure phase of barium tungstate obtained in S8.1 is put into a mortar for grinding to obtain fine first particles; then granulation is performed, which is also performed in the mortar, that is, 10% PVA binder is added in small amounts several times during the grinding process to obtain second particles; after granulation, the obtained second particles are sieved with 80 mesh and 120 mesh to obtain third particles of 80-120 mesh; the third particles are weighed with a balance, and the mass is 0.6-0.8g; then the weighed third particles are put into a tablet press, the pressure is 6-15MPa, and the time is 1-3min to obtain barium tungstate sample tablets.

[0157] S8.3. Preparation of barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction at different temperature gradients.

[0158] Specifically, the barium tungstate sample sheet was placed in a crucible and calcined at different temperatures in a muffle furnace. First, the temperature was increased to 600°C at a heating rate of 5°C / min and kept at this temperature for 2 hours. Then, the temperature was increased to 1050°C at the same heating rate and kept at this temperature for 2 hours to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0159] The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention is used as a catalyst, and the specific steps are: the prepared barium tungstate ceramic self-catalytic electrode material is clamped on a platinum electrode clamp directly as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The electrochemical performance of HER is tested in a 1.0M KOH solution at room temperature and pressure.

[0160] Embodiment 9

[0161] The embodiment of the present invention provides another specific method for preparing a barium tungstate ceramic autocatalytic electrode for efficient hydrogen evolution reaction based on the first embodiment. The preparation method comprises:

[0162] S9.1. Prepare pure phase of barium tungstate by solid phase method.

[0163] Specifically, first, 0.025 mol of barium carbonate and 0.020 mol of tungsten trioxide are mixed in equal molar amounts to obtain a first mixed drug; deionized water and zirconium balls are added to the first mixed drug according to a certain mass ratio to obtain a second mixed drug, zirconium balls: first mixed drug: deionized water = 4:1:1, zirconium balls are 40-50g, deionized water is 10-15mL; then the second mixed drug is put into a ball mill for ball milling, the ball milling time is 4-10h, the speed is 300 rpm, and a mixed solution is obtained. The mixed solution obtained after ball milling is poured into a glass dish and dried in an oven at a temperature of 80°C for 3-6h; the dried sample is sieved to remove the zirconium balls in the sample to obtain a sample powder; then the sample powder is put into a crucible, and the temperature is raised to 860°C at a rate of 2°C / min in a muffle furnace, and kept warm for 6h to obtain a pure phase of barium tungstate.

[0164] S9.2. Granulate and tablet the pure phase of barium tungstate.

[0165] Specifically, the pure phase of barium tungstate obtained in S9.1 is put into a mortar for grinding to obtain fine first particles; then granulation is performed, which is also performed in the mortar, that is, 10% PVA binder is added in small amounts several times during the grinding process to obtain second particles; after granulation, the obtained second particles are sieved with 80 mesh and 120 mesh to obtain third particles of 80-120 mesh; the third particles are weighed with a balance, and the mass is 0.6-0.8g; then the weighed third particles are put into a tablet press, the pressure is 6-15MPa, and the time is 1-3min to obtain barium tungstate sample tablets.

[0166] S9.3. Preparation of barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction at different temperature gradients.

[0167] Specifically, the barium tungstate sample sheet was placed in a crucible and calcined at different temperatures in a muffle furnace. First, the temperature was increased to 600°C at a heating rate of 5°C / min and kept at this temperature for 2 hours. Then, the temperature was increased to 1075°C at the same heating rate and kept at this temperature for 2 hours to obtain a barium tungstate ceramic self-catalytic electrode for efficient hydrogen evolution reaction.

[0168] The barium tungstate ceramic self-catalytic electrode material for efficient hydrogen evolution reaction prepared by the present invention is used as a catalyst, and the specific steps are: the prepared barium tungstate ceramic self-catalytic electrode material is clamped on a platinum electrode clamp directly as a working electrode, a mercury oxide electrode is used as a reference electrode, and a carbon rod is used as a counter electrode. The electrochemical performance of HER is tested in a 1.0M KOH solution at room temperature and pressure.

[0169] See also Fig. 9 , Fig. 9 Actual photos of the barium tungstate ceramic self-catalytic electrode obtained by calcining at 1050℃, 1075℃ and 1100℃ respectively.

[0170] In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of the present invention, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0171] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine different embodiments or examples described in this specification.

[0172] Although the present invention is described herein in conjunction with various embodiments, in the process of implementing the claimed invention, those skilled in the art may understand and implement other variations of the disclosed embodiments by viewing the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other components or steps, and "one" or "an" does not exclude multiple situations. A single processor or other unit may implement several functions listed in the claims. Certain measures are recorded in different dependent claims, but this does not mean that these measures cannot be combined to produce good results.

[0173] The above contents are further detailed descriptions of the present invention in combination with specific preferred embodiments, and it cannot be determined that the specific implementation of the present invention is limited to these descriptions. For ordinary technicians in the technical field to which the present invention belongs, any modifications made without departing from the concept of the present invention should be deemed to belong to the protection scope of the present invention.

Claims

1. An application of a barium tungstate ceramic material as an autocatalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: The preparation method of the barium tungstate ceramic self-catalytic electrode comprises: Based on the solid phase method, pure phase barium tungstate is prepared using barium carbonate and tungsten trioxide chemicals; The pure phase of barium tungstate is sequentially granulated and tabletted, and a PVA binder is added dropwise during granulation to obtain a barium tungstate sample sheet; Calcining the barium tungstate sample sheet at a first temperature to expel PVA and obtain a calcined barium tungstate sample sheet; The calcined barium tungstate sample sheet is calcined at a second temperature to form a ceramic phase in the barium tungstate sample sheet, thereby obtaining a barium tungstate ceramic self-catalytic electrode, wherein the second temperature is greater than the first temperature.

2. The use of the barium tungstate ceramic material according to claim 1 as a self-catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: Based on the solid phase method, pure phase barium tungstate is prepared using barium carbonate and tungsten trioxide chemicals, including: Mixing the barium carbonate drug and the tungsten trioxide drug according to a preset molar ratio to obtain a first mixed drug; Adding deionized water and zirconium balls to the mixed medicine according to a preset ratio to obtain a second mixed medicine; ball milling the second mixed medicine to obtain a mixed solution; Drying the mixed solution to obtain a dried sample; The dried sample is sieved to remove zirconium balls in the sample to obtain sample powder; The sample powder is calcined to obtain the pure phase of barium tungstate.

3. The use of the barium tungstate ceramic material according to claim 2 as a self-catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: The preset molar ratio is that the molar ratio of barium carbonate to tungsten trioxide is 1:0.8~1.

2.

4. The use of the barium tungstate ceramic material according to claim 2 as a self-catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: The preset ratio is that the mass ratio of deionized water, the first mixed medicine and the zirconium balls is 4:1:

1.

5. The use of the barium tungstate ceramic material according to claim 2 as a self-catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: The sample powder is calcined to obtain the pure phase of barium tungstate, including: The sample powder is placed in a crucible, and the temperature is raised to 850-900°C at a rate of 2-5°C / min in a muffle furnace. The sample powder is kept at 850-900°C for 6-10 h to obtain the pure phase of barium tungstate.

6. The use of the barium tungstate ceramic material according to claim 1 as a self-catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: The pure phase of barium tungstate is granulated and tabletted in sequence to obtain a barium tungstate sample tablet, comprising: Grinding the pure phase of barium tungstate to obtain first particles; During the grinding process, a PVA binder is added dropwise to the first particles for multiple times to obtain second particles; The second particles are sieved to obtain third particles with a mesh size of 80 to 120; Weigh 0.6-0.8 g of the third particle; Under a pressure of 6-15 MPa, the weighed third particles are pressed for 1-3 min to obtain the barium tungstate sample sheet.

7. The use of the barium tungstate ceramic material according to claim 6 as a self-catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: During the grinding process, a PVA binder is added to the first particles multiple times to obtain second particles, comprising: During the grinding process, one drop of the PVA binder is added to the first particles every 2 to 5 minutes to obtain the second particles, wherein the total amount of the PVA binder added is 3 to 8 ml, and the total adding time is 1 to 2 hours.

8. The use of the barium tungstate ceramic material according to claim 1 as a self-catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: The barium tungstate sample sheet is calcined at a first temperature to expel PVA, thereby obtaining a calcined barium tungstate sample sheet, comprising: The barium tungstate sample piece is placed in a crucible, and the temperature is raised to 600-800°C at a rate of 2-5°C / min in a muffle furnace, and the barium tungstate sample piece is kept at 600-800°C for 2-5 hours to obtain the calcined barium tungstate sample piece.

9. The use of the barium tungstate ceramic material according to claim 1 as a self-catalytic electrode for electrolysis of water for hydrogen evolution, characterized in that: The calcined barium tungstate sample sheet is calcined at a second temperature to form a ceramic phase on the barium tungstate sample sheet to obtain a barium tungstate ceramic self-catalytic electrode, comprising: The calcined barium tungstate sample piece is placed in a crucible, and the temperature is raised to 1075°C in a muffle furnace at a rate of 2-5°C / min. The calcined barium tungstate sample piece is kept at 1075°C for 2-5 hours to obtain the barium tungstate ceramic self-catalytic electrode.

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